U.S. patent application number 11/857795 was filed with the patent office on 2008-01-10 for polymer particles and methods for their preparation and use.
Invention is credited to Cory Michael Bryant, Lewis Michael Popplewell.
Application Number | 20080009559 11/857795 |
Document ID | / |
Family ID | 32990568 |
Filed Date | 2008-01-10 |
United States Patent
Application |
20080009559 |
Kind Code |
A1 |
Popplewell; Lewis Michael ;
et al. |
January 10, 2008 |
Polymer Particles and Methods for Their Preparation and Use
Abstract
A particle composition comprising a water-soluble carrier such
as starch, a structuring agent such as an ester terminated
polyamide and fragrance or flavor is disclosed. Methods of making
and using the particles are also disclosed. The particles are
desirable for providing fragrance to various products such as
powdered detergents.
Inventors: |
Popplewell; Lewis Michael;
(Morganville, NJ) ; Bryant; Cory Michael; (New
York, NY) |
Correspondence
Address: |
INTERNATIONAL FLAVORS & FRAGRANCES INC.
521 WEST 57TH ST
NEW YORK
NY
10019
US
|
Family ID: |
32990568 |
Appl. No.: |
11/857795 |
Filed: |
September 19, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10434981 |
May 9, 2003 |
|
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11857795 |
Sep 19, 2007 |
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Current U.S.
Class: |
523/100 ;
523/102 |
Current CPC
Class: |
A61Q 13/00 20130101;
A61K 8/11 20130101; A61K 8/732 20130101; A61Q 15/00 20130101; C11D
3/505 20130101; A61K 2800/412 20130101; A61K 8/88 20130101; A61Q
5/02 20130101 |
Class at
Publication: |
523/100 ;
523/102 |
International
Class: |
C08J 3/20 20060101
C08J003/20 |
Claims
1. A method for making the particle composition wherein a water
soluble carrier is added to a suitable solvent to form a first
admixture; a structuring agent is added to a fragrance or flavor to
form a second admixture; the first and second admixtures are
combined while being subjected to high speed mixing or
homogenization; and drying the final admixture to form a
particle.
2. The method of claim 1 wherein the particle formed has a particle
size of from about 30 to about 80 microns.
3. The method of claim 1 wherein a clay material is added to the
water soluble carrier.
4. The method of claim 1 wherein the water soluble carrier is
starch and the level of starch is from about 25 to about 75% of the
particle.
5. The method of claim 1 wherein the structuring agent is an ester
terminated polyamide.
6. The method of claim 5 wherein the level of ester terminated
polyamide is from about 5 to about 40 weight percent of the
particle.
7. The method of claim 1 wherein the particle formed has a
fragrance level from about 5 to about 30 weight percent of the
particle.
8. The method of claim 1 wherein discrete beads comprising the
structuring agent and flavor or fragrance materials are formed in
the water-soluble carrier.
9. The method of claim 8 wherein the structuring agent is an ester
terminated polyamide.
Description
RELATED APPLICATIONS
[0001] This application is a divisional application of U.S.
application Ser. No. 10/434,981 filed May 9, 2003, now pending.
FIELD OF INVENTION
[0002] The invention relates to particles containing starches or
other water soluble carriers, ester terminated polyamides or other
hydrophobic structuring materials and fragrances or flavors, as
well as methods for the preparation and use of such particles.
BACKGROUND OF THE ART
[0003] In recent years, the food, cosmetics, and fragrance
industries have found interest in encapsulated products. Such
products allow incorporation of fragrance in small distinct
packages that can be dispersed throughout a dispersion medium. Such
encapsulated products are generally formed from carriers or
encapsulants that are not miscible or compatible with the active
agent. For example, hydrophilic substances are often used to
surround and encapsulate hydrophobic substances. This type of
particle is a core-shell type particle, or in some cases a
multi-core type particle. As suggested by the name, two discrete
phases make up the particle. The core and shell are each maintained
as individual components rather than a continuous phase.
[0004] Most encapsulated flavors or fragrances are formed via spray
drying. Spray drying typically involves the use of water-soluble
polymeric encapsulants such as gum arabic, modified starch, and/or
dextrin as the main carrier materials. These materials are often
used in combination with varying amounts of plasticizers, gellants,
and surface-active polymers to control processing, and more
importantly, product characteristics. As discussed above, the
flavor or fragrance to be encapsulated is normally not miscible
with the water-soluble carrier system selected, although some
flavor and fragrance materials can plasticize the carriers
appreciably. Many variations of spray-dried carriers are used by
those familiar with the art to control product stability and
release. These variations focus almost exclusively on the water
soluble carrier and its properties in the dry state, or on control
of the kinetic process of hydration/dissolution, as opposed to
attempting to control the release of flavor or fragrance once the
carrier is dissolved.
[0005] A continuing challenge in the area of flavor and fragrance
delivery, then, is the identification of encapsulation systems that
provide release characteristics suitable for a specific application
and environment.
SUMMARY OF THE INVENTION
[0006] A particle composition comprising discrete particles
containing fragrances or flavors, ester terminated polyamide
(ETPA), or other similarly functional structuring materials, and
water-soluble carriers is described herein.
[0007] In a preferred embodiment, the particles comprise from about
20 to about 90 weight percent carrier, structuring material from
about 5 to about 40 weight percent and fragrance or flavor from
about 5 to about 40 weight percent on a dry basis. The particles
are preferably formed by creating a mixture of water soluble
carrier in a solvent, preferably water, preferably at an elevated
temperature. A second mixture is formed by mixing the structuring
material and flavor or fragrance, preferably with heating. The two
mixtures are then admixed, preferably under high shear mixing or
homogenization to form a dispersion and the particles are then
obtained by drying.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 is a depiction of a single particle of the carrier
material with the fragrance and ETPA distributed throughout the
particle.
[0009] FIG. 2 is a graphical presentation of the average intensity
of the headspace odor emitted above an open wash basin containing
cloth that is soaking in detergent containing added fragrance
particles.
DETAILED DESCRIPTION
[0010] The invention essentially consists of the surprising
discovery that specific hydrophobic, meltable polymers/materials
can be used to create discrete polymer-flavor/fragrance beads
within a dried water-soluble carrier. The discrete polymer
particles are distributed throughout a continuous phase of
water-soluble carrier. Particles with this structure provide two
main, useful, benefits. First, the water-soluble carrier can be
designed to provide appropriate protection to the volatile, or
otherwise sensitive flavor/fragrance materials. Second, the
structured beads, once released from the carrier via its
dissolution, control diffusion of the flavor/fragrance into the
surrounding environment. In a preferred embodiment, spray drying is
used to form the particles since the steps of emulsion formation
and drying are fundamental characteristics of the process. Another
preferred embodiment provides the use of ETPA as the structuring
agent, as it has a high affinity for fragrances, and can
effectively control their evaporation/diffusion. A further
advantage of the use of ETPA is that it is a meltable polymer
allowing further protection of a fragrance material when employed
in heated environments found in situations such as laundering of
clothing.
[0011] The water-soluble carrier used in this invention includes
starches, dextrins, hydrocolloids, low molecular weight
plasticizers, and surface active agents. Starch, as used in this
application, includes starch, chemically modified starch,
maltodextrin and the like. Suitable hydrocolloid materials include
gum arabic, cellulosic polymers, gelatin and alginates; suitable
low molecular weight plasticizers include polyols such as
glycerine, sugars such as sucrose and dextrin; and suitable surface
active agents include pluronic polyols, polysorbates, lecithins,
ethoxylates, laurates, oleates, stearates, and lactylates. As those
with skill in the art recognize, a mixture of carrier materials
appropriate for the particular application can be employed in the
present invention.
[0012] The dried particles of the present invention contain from
about 20 to about 90 weight percent water soluble carrier,
preferably starch, preferably from about 30 to about 80 and most
preferably from about 40 to about 70 weight percent starch or
carrier materials.
[0013] The preferred structuring agents used in the present
invention include waxes, fats and ETPA. The common characteristics
of these materials are that they are normally crystalline, when
above their melting point are reasonably soluble in the flavor or
fragrance, and upon cooling substantially re-crystallize in the
presence of the flavor or fragrance. The re-crystallization creates
the structured flavor/fragrance bead embedded within the soluble
carrier. Of course, other structuring materials which create a bead
via a substantial increase in viscosity without re-crystallization
may also be used, but are less preferred.
[0014] Ester terminated polyamides (ETPA) are disclosed in U.S.
Pat. Nos. 5,783,657; 5,998,570; 6,111,055; 6,214,063 and 6,268,466,
the contents or which are incorporated by reference as if set forth
in their entirety. Similarly, amide terminated polyamides (ATPA)
are disclosed in U.S. Pat. No. 6,268,466, the contents of which is
incorporated by reference. Both ETPA and ATPA are commercially
available materials from Arizona Chemical, of Jacksonville, Fla. As
used throughout the attached specification and claims ETPA is meant
to include ETPA, ATPA and mixtures of ETPA and ATPA.
[0015] Other meltable structuring materials that may be used in the
present invention to create the internal flavor/fragrance bead
phase include triglycerides that melt above approximately
25.degree. C., waxes such as beeswax, carnauba wax, paraffin waxes;
stearyl alcohol, and low molecular weight polyethylene. Highly
desirable properties of these materials are that they melt or
soften sufficiently at temperatures below about 120.degree. C. in
order to promote gentle combination with flavor/fragrance
materials, that they form a largely continuous phase with
flavor/fragrance materials once melted or softened, and that they
form a reasonably solid structure with substantial amounts of
entrapped fragrance/flavor once cooled to ambient temperature.
These properties jointly allow for the efficient incorporation of
flavor/fragrance, as well as the desired structural and controlled
release characteristics.
[0016] The level of structuring agent, such as ETPA, provided in
the dried particles of the invention is from about 10 to about 40
weight percent of the particle, preferably from about 15 to about
35 and most preferably from about 20 to about 30 weight percent of
the particle.
[0017] Many types of fragrances can be employed in the present
invention, the only limitation being the compatibility with the
other components being employed. Suitable fragrances include but
are not limited to fruits such as almond, apple, cherry, grape,
pear, pineapple, orange, strawberry, raspberry; musk, flower scents
such as lavender-like, rose-like, iris-like, and carnation-like.
Other pleasant scents include herbal and woodland scents derived
from pine, spruce and other forest smells. Fragrances may also be
derived from various oils, such as essential oils, or from plant
materials such as peppermint, spearmint and the like.
[0018] A list of suitable fragrances is provided in U.S. Pat. No.
4,534,891, the contents of which are incorporated by reference as
if set forth in its entirety. Another source of suitable fragrances
is found in Fragrances, Cosmetics and Soaps, Second Edition, edited
by W. A. Poucher, 1959. Among the fragrances provided in this
treatise are acacia, cassie, chypre, cyclamen, fern, gardenia,
hawthorn, heliotrope, honeysuckle, hyacinth, jasmine, lilac, lily,
magnolia, mimosa, narcissus, freshly-cut hay, orange blossom,
orchid, reseda, sweet pea, trefle, tuberose, vanilla, violet,
wallflower, and the like.
[0019] As used herein, olfactory effective amount is understood to
mean the level of the fragrance-containing particles that will
contribute its particular olfactory characteristics to a product.
The olfactory effect of the composition will be the sum of the
effects of each of the fragrance or fragrance ingredients including
the fragrance-containing particles or fragrance-containing
particles of the present invention. Thus, the particles of the
invention can be used to alter the aroma characteristics of a
product or fragrance composition by modifying the olfactory
reaction contributed by another ingredient in the product or
fragrance. Similarly, when flavors are employed the level of
encapsulated flavor particles of the invention will vary depending
on many factors including other ingredients, their relative amounts
and the effect that is desired. Those with skill in the art will
incorporate suitable materials in the invention when the product
incorporating the present invention is intended for human or animal
consumption.
[0020] Suitable conventional flavoring materials include saturated
fatty acids, unsaturated fatty acids and amino acids; alcohols,
including primary and secondary alcohols; esters; carbonyl
compounds including ketones and aldehydes; lactones; other cyclic
organic materials including benzene derivatives, acyclic compounds,
heterocyclics such as furans, pyridines, pyrazines and the like;
sulfur-containing compounds including thiols, sulfides, disulfides
and the like; proteins; lipids, carbohydrates; so-called flavor
potentiators such as monosodium glutamate, magnesium glutamate,
calcium glutamate, guanylates and inosinates; natural flavoring
materials such as cocoa, vanilla and caramel; essential oils and
extracts such as anise oil, clove oil and the like and artificial
flavoring materials such as vanillin, ethyl vanillin and the
like.
[0021] Specific preferred flavor adjuvants include, but are not
limited to, the following: anise oil; ethyl-2-methyl butyrate;
vanillin; cis-3-heptenol; cis-3-hexenol; trans-2-heptenal; butyl
valerate; 2,3-diethyl pyrazine; methyl cyclo-pentenolone;
benzaldehyde; valerian oil; 3,4-dimeth-oxyphenol; amyl acetate;
amyl cinnamate; .gamma.-butyryl lactone; furfural; trimethyl
pyrazine; phenyl acetic acid; isovaleraldehyde; ethyl maltol; ethyl
vanillin; ethyl valerate; ethyl butyrate; cocoa extract; coffee
extract; peppermint oil; spearmint oil; clove oil; anethol;
cardamom oil; wintergreen oil; cinnamic aldehyde; ethyl-2-methyl
valerate; .gamma.-hexenyl lactone; 2,4-decadienal; 2,4-heptadienal;
methyl thiazole alcohol (4-methyl-5-.beta.-hydroxyethyl thiazole);
2-methyl butanethiol; 4-mercapto-2-butanone;
3-mercapto-2-pentanone; 1-mercapto-2-propane; benzaldehyde;
furfural; furfuryl alcohol; 2-mercapto propionic acid; alkyl
pyrazine; methyl pyrazine; 2-ethyl-3-methyl pyrazine; tetramethyl
pyrazine; polysulfides; dipropyl disulfide; methyl benzyl
disulfide; alkyl thiophene; 2,3-dimethyl thiophene; 5-methyl
furfural; acetyl furan; 2,4-decadienal; guiacol; phenyl
acetaldehyde; .beta.-decalactone; d-limonene; acetoin; amyl
acetate; maltol; ethyl butyrate; levulinic acid; piperonal; ethyl
acetate; n-octanal; n-pentanal; n-hexanal; diacetyl; monosodium
glutamate; monopotassium glutamate; sulfur-containing amino acids,
e.g., cysteine; hydrolyzed vegetable protein;
2-methylfuran-3-thiol; 2-methyldihydrofuran-3-thiol;
2,5-dimethylfuran-3-thiol; hydrolyzed fish protein; tetramethyl
pyrazine; propylpropenyl disulfide; propylpropenyl trisulfide;
diallyl disulfide; diallyl trisulfide; dipropenyl disulfide;
dipropenyl trisulfide;
4-methyl-2-[(methylthio)-ethyl]-1,3-dithiolane;
4,5-dimethyl-2-(methylthiomethyl)-1,3-dithiolane; and
4-methyl-2-(methylthiomethyl)-1,3-dithiolane. These and other
flavor ingredients are provided in U.S. Pat. Nos. 6,110,520 and
6,333,180 hereby incorporated by reference.
[0022] The level of flavor or fragrance employed in the dry
particle of the invention varies from about 5 to about 40 weight
percent, preferably from about 15 to about 30 and most preferably
from about 20 to about 25 weight percent.
[0023] In addition to the carrier, structuring material, and
fragrance or flavor, other agents can be added to the particles by
incorporation into the fragrance, structuring material, or the
carrier. Well known materials such as solvents, surfactants and
emulsifiers for the fragrance/flavor--structuring material mixture
can be employed without departing from the scope of the present
invention. Additionally, positively charged polymers can be added
to either phase of the particle to promote deposition on hair,
skin, cloth, or other negatively charged substrates. These
materials include modified starches, quaternary salts, cationic
guar gum, hydroxyl ethyl cellulose, and cationic silicones.
[0024] Optionally, functional materials such as hydrocolloids and
other water-soluble polymers may be added to lend certain desired
characteristics to the particle, such as creating a viscous
micro-environment in aqueous solutions which can enhance particle
integrity and reduce flavor/fragrance diffusion. Suitable
hydrocolloids and other water-soluble polymers include gum arabic,
alginate, carageenan and gelatin. The level of the functional
carrier materials is from about 0.1 to about 20 weight percent on a
dry basis, preferably from about 1 to about 10 weight percent and
most preferably from about 2 to about 5 weight percent of the
particle weight.
[0025] According to one embodiment of the invention, the carrier
material is dissolved in a suitable solvent, commonly water. This
action may form a true solution, as noted by clarity and lack of a
precipitate, or may result in a form that may more properly be
referred to as a sol, or a somewhat imperfect solution. The term
"solution" used throughout this specification is meant to encompass
each of these situations.
[0026] The most preferred drying method is spray drying, although
other solvent removal techniques can be used.
[0027] Referring to FIG. 1, particle 10 is depicted as made in a
spherical shape. A spherical shape is commonly achieved by a spray
drying process. FIG. 1 depicts the shell is comprised of a
continuous water soluble material 15 such as a starch and the
structuring material and fragrance such as ETPA--fragrance mixture
or flavor mixture 20 as discrete phases located throughout the
continuous water soluble material phase.
[0028] Particle size can vary depending on the conditions used to
dry the particles, but the particle size generally ranges from
about 10 to about 200 microns and more preferably from about 30 to
about 100 microns. The size of the discrete flavor/fragrance
particles within the particle are commonly from about 0.1 to about
25 microns, preferably from about 5 to about 20 microns. After the
drying process is complete a grinding or sizing process can be
employed if desired to achieve a more consistent and narrower
particle size distribution.
[0029] The inventive particles are suitable for incorporation into
many products. Some non-limiting examples include cosmetics,
cleaning products such as bleaches, cleansers, detergents,
shampoos, etc. As can be appreciated, the preferred embodiments
will lend themselves to the use of powdered materials containing
the particles of the invention. In a highly preferred embodiment,
the powdered product is a laundry detergent.
[0030] The amount of the particles added to a product varies
depending on the amount of fragrance that one might want to impart
to a product. The level of particle can vary from about 0.5 up to
about 20 weight percent of the product, preferably from about 1 to
about 10 weight percent of the product.
[0031] The present invention is advantageously used in applications
such as laundry detergents because the starch shell is soluble in
water, and the structuring agent, such as ETPA is well suited for
kinetically controlling fragrance release. For example, the ETPA
aids in protecting the fragrance so that it can be delivered at a
later or more appropriate time in the product usage. When a flavor
is employed, the particles of the present invention can be added
alone or with other spices and flavoring, with baking powders and
baking sodas or in any other application in which a powder is added
to a foodstuff. Suitable food products that that can employ the
present invention include but are not limited to soups, salad
dressings and yogurts.
[0032] Unless noted to the contrary, all percentages are given on a
weight percent on a dry basis, and all temperatures are in
Centigrade. The following examples are not meant to define or
otherwise limit the scope of the invention. Rather the scope of the
invention is to be ascertained according to the claims that follow
the examples.
EXAMPLE 1
[0033] A spray dried fragrance-containing material was prepared
using the following materials: [0034] 300 grams deionized water;
[0035] 120 grams CAPSUL starch [National Starch and Chemical
Company]; [0036] 40 grams of ETPA [Arizona Chemical]; and [0037] 40
grams of a fragrance formulation.
[0038] A preblend of starch and water was formed at 70.degree. C.
The fragrance oil and ETPA were mixed separately at 80.degree. C.
and then added to the starch solution. The materials were blended
for 2 minutes at 80.degree. C. before spray drying on an Armfield
spray dryer while maintaining temperature of 80.degree. C. on the
solution. 168 Grams of dry powder was obtained.
EXAMPLE 2
[0039] A spray dried fragrance-containing material was prepared
using the following materials: [0040] 280 grams deionized water;
[0041] 112 grams M100 maltodextrin [available from Grain Processing
Corporation]; [0042] 28 grams gum Arabic [Colloides Naturels Inc.];
[0043] 20 grams of ETPA [Arizona Chemical]; and [0044] 40 grams of
a predominately aldehyde-containing fragrance formulation.
[0045] A preblend of M100, gum arabic and water was formed at
70.degree. C. The fragrance oil and ETPA were mixed separately at
80.degree. C. and then added to the M100, gum arabic solution at
80.degree. C. until the ETPA was melted. The materials were
homogenized for 5 minutes before spray drying on an Armfield spray
dryer. 166 Grams of dry powder was obtained.
EXAMPLE 3
[0046] A spray dried fragrance-containing material was prepared
using the following materials: [0047] 320 grams deionized water;
120 grams CAPSUL starch [National Starch and Chemical Company];
[0048] 40 grams of ETPA [Arizona Chemical]; and [0049] 40 grams of
a fragrance formulation.
[0050] A preblend of starch and water was formed at 70.degree. C.
The fragrance oil and ETPA were mixed separately at 80.degree. C.
until melted and then added to the starch solution. The materials
were homogenized for 5 minutes at 80.degree. C. before spray drying
on an Armfield spray dryer while maintaining a temperature of
80.degree. C. on the solution. 161 Grams of dry powder was
obtained.
EXAMPLE 4
[0051] A spray dried fragrance-containing material was prepared
using the following materials: [0052] 300 grams deionized water;
[0053] 120 grams CAPSUL starch [National Starch and Chemical
Company]; [0054] 40 grams of ETPA [Arizona Chemical]; [0055] 20
grams of clay; and [0056] 40 grams of a fragrance formulation.
[0057] A preblend of starch, clay and water was formed at
70.degree. C. The fragrance formulation and ETPA were mixed
separately at 80.degree. C. and then added to the starch solution.
The materials were homogenized for 10 minutes at 80.degree. C.
before spray drying. 133 Grams of dry powder was obtained.
EXAMPLE 5
[0058] A spray dried fragrance-containing material was prepared
using the following materials: [0059] 300 grams deionized water;
[0060] 100 grams CAPSUL starch [0061] 30 grams of ETPA [Arizona
Chemical]; [0062] 30 grams of Neobee [Stepan Company]; and [0063]
40 grams of a fragrance formulation.
[0064] A preblend of starch and water was formed at 70.degree. C.
The fragrance formulation, Neobee and ETPA were mixed separately at
80.degree. C. and then added to the starch solution. The materials
were homogenized for 10 minutes at 80.degree. C. before spray
drying. 172 Grams of dry powder was obtained.
EXAMPLE 6
[0065] The particles of Example 1, containing ETPA, starch and
fragrance, were added to a commercial fragrance-free powder
detergent. Clothes were washed with a commercial detergent and the
same commercial detergent with the composition of the present
invention.
[0066] Panelists were asked to compare the fragrance imparted to
the clothes soaking in a wash basin containing water plus the
commercial product alone as compared to the commercial product and
the present invention together. The products were provided such
that the control, the commercial detergent, contained the same
level of fragrance as the commercial detergent and the
fragrance-containing particles of the present invention. Clothes
were washed under identical conditions using the two detergent
systems. FIG. 2 displays the results of this evaluation. Neat
indicates that the detergent did not include the particles of the
present invention. Neat+particles indicates that the detergent also
contained the particles of the present invention. Results indicate
that with increasing soak time the particles imparted a fragrance
with a longer-lasting and more powerful bloom.
[0067] Panelists were then asked to compare the fragrance imparted
to the washed, undried clothes. The damp clothes were evaluated by
20 panelists. More than 80 percent of the panelists chose the
clothes laundered in the detergent and the particles of the present
invention compared to a control detergent containing the same level
of fragrance.
[0068] As noted, the above description is a non-limiting example of
certain preferred particles of the invention and methods for making
them. Other obvious variants will be apparent to those skilled in
the art without parting from the scope and spirit of the invention
as claimed herein.
* * * * *